WO2015133587A1 - Working medium for heat cycle, and heat cycle system - Google Patents

Abstract

　To provide a heat cycle system having excellent cycle performance and safety, whereby a working medium thereof is incombustible and ozone layer or global warming effects are low even when the working medium is leaked. A heat cycle system which uses a working medium including trifluoroethylene and 1,1,1,2-tetrafluoroethane and/or pentafluoroethane, the ratio of trifluoroethylene in a gas phase formed in the system being 50% by mass or less. For example, a refrigeration cycle system (10) having a compressor (11), a condenser (12), an expansion valve (13), and an evaporator (14), the working medium thereof being controlled as described above.

Description

Working medium for heat cycle and heat cycle system

The present invention relates to a working medium for heat cycle and a heat cycle system.

Thermal cycle systems used for refrigerators, air conditioners, power generation systems (waste heat recovery power generation, etc.), latent heat transport devices (heat pipes, etc.), etc. Those using HFC) are known. However, it has been pointed out that HFC may cause global warming. For example, 1,1,1,2-tetrafluoroethane (HFC-134a) used as a refrigerant for automobile air conditioners has a large global warming potential of 1430 (100-year value).

A thermal cycle system using hydrofluoroolefin (hereinafter referred to as HFO) has been proposed as a thermal cycle system using a working medium that has little influence on the ozone layer and little influence on global warming. . HFO has little influence on the ozone layer, and has a carbon-carbon double bond that is easily decomposed by OH radicals in the atmosphere, and therefore has little influence on global warming.

Specifically, the following thermal cycle systems (1) to (3) can be mentioned.
(1) 3,3,3-trifluoropropene (HFO-1243zf), 1,3,3,3-tetrafluoropropene (HFO-1234ze), 2-fluoropropene (HFO-1261yf), 2,3,3 Cycle system using a working medium containing 1,3,4-tetrafluoropropene (HFO-1234yf), 1,1,2-trifluoropropene (HFO-1243yc) and the like (Patent Document 1).
(2) 1,2,3,3,3-pentafluoropropene (HFO-1225ye), trans-1,3,3,3-tetrafluoropropene (HFO-1234ze (E)), cis-1,3,3 A thermal cycle system using a working medium containing 3,3-tetrafluoropropene (HFO-1234ze (Z)), HFO-1234yf and the like (Patent Document 2).
(3) A thermal cycle system using a working medium containing trifluoroethylene (HFO-1123) (Patent Document 3).

JP-A-4-110388 JP-T-2006-512426 International Publication No. 2012/157774

However, both the thermal cycle systems (1) and (2) have insufficient cycle performance (capability).
In addition, although the thermal cycle system (3) provides excellent cycle performance, the HFO-1123 used has combustibility. For example, in an automotive air conditioner or the like, the working medium may leak from the connection hose, bearing portion, etc., so the gas phase working medium formed in the system leaks, the working medium mixes with air, It is important to ensure the safety of the system by using a working medium that does not spread easily even if it ignites.

INDUSTRIAL APPLICABILITY The present invention is nonflammable, has little influence on the ozone layer and global warming even if leaked, has excellent cycle performance, and is excellent in safety. Therefore, an object of the present invention is to provide a thermal cycle system which has little influence on the ozone layer and global warming even when leaked, has excellent cycle performance, and is excellent in safety.

The working medium for heat cycle of the present invention includes trifluoroethylene (hereinafter referred to as HFO-1123), 1,1,1,2-tetrafluoroethane (hereinafter referred to as HFC-134a), and pentafluoroethane. (Hereinafter referred to as HFC-125), wherein the ratio of HFO-1123 to the total mass of the working medium is 42% by mass or less. And
In the thermal cycle working medium of the present invention, the ratio of the total amount of HFC-134a and HFC-125 to the total mass of the thermal cycle working medium is preferably 58% by mass or more.

The working medium for heat cycle of the present invention includes HFO-1123, HFC-134a, HFC-125, and 2,3,3,3-tetrafluoropropene (hereinafter referred to as HFO-1234yf). The ratio of the total amount of HFO-1123, HFC-134a, HFC-125, and HFO-1234yf to the total mass of the working medium is more than 90% by mass and not more than 100% by mass, and HFO- The ratio of HFO-1123 to the total amount of 1123, HFC-134a, HFC-125, and HFO-1234yf is 3 mass% to 35 mass%, the ratio of HFC-134a is 10 mass% to 53 mass%, HFC The ratio of -125 is 4 mass% to 50 mass%, and the ratio of HFO-1234yf is 5 mass% to 50 mass%. Rukoto is preferable.
Furthermore, the ratio of HFO-1123 to the total amount of HFO-1123, HFC-134a, HFC-125, and HFO-1234yf is 6% by mass to 25% by mass, and the ratio of HFC-134a is 20% by mass to 35% by mass. %, HFC-125 is preferably 8% by mass to 30% by mass, and HFO-1234yf is preferably 20% by mass to 50% by mass.
Moreover, it is preferable that the global warming potential of the working medium for heat cycle is 2000 or less.

A thermal cycle system according to the present invention is a thermal cycle system using a thermal cycle working medium including HFO-1123 and one or both of HFC-134a and HFC-125, and the thermal cycle system includes The ratio of HFO-1123 in the formed gas phase is 50% by mass or less.
In the thermal cycle system of the present invention, the ratio of HFO-1123 to the total mass of the working medium in the system is preferably 42% by mass or less.
The ratio of the total amount of HFC-134a and HFC-125 to the total mass of the working medium in the system is preferably 58% by mass or more.

The thermal cycle system of the present invention is a thermal cycle system using a thermal cycle working medium including HFO-1123, HFC-134a, HFC-125, and HFO-1234yf, and is based on the total mass of the working medium. The ratio of the total amount of HFO-1123, HFC-134a, HFC-125, and HFO-1234yf is more than 90% by mass and 100% by mass or less,
The ratio of HFO-1123 to 3 mass% to 35 mass% and the ratio of HFC-134a to 10 mass% to 53 mass% with respect to the total amount of HFO-1123, HFC-134a, HFC-125, and HFO-1234yf The ratio of HFC-125 is preferably 4% by mass or more and 50% by mass or less, and the ratio of HFO-1234yf is preferably 5% by mass or more and 50% by mass or less.
Furthermore, the ratio of HFO-1123 to the total amount of HFO-1123, HFC-134a, HFC-125, and HFO-1234yf is 6% by mass to 25% by mass, and the ratio of HFC-134a is 20% by mass to 35% by mass. %, HFC-125 is preferably 8% by mass to 30% by mass, and HFO-1234yf is preferably 20% by mass to 50% by mass.
Moreover, it is preferable that the global warming potential of the working medium for heat cycle is 2000 or less.

The heat cycle system of the present invention is preferably used for a refrigeration / refrigeration device, an air conditioner, a power generation system, a heat transport device, or a secondary cooler.
The heat cycle system of the present invention includes a room air conditioner, a store packaged air conditioner, a building packaged air conditioner, a facility packaged air conditioner, a gas engine heat pump, a train air conditioner, an automobile air conditioner, a built-in showcase, and a separate showcase. It is preferably used for a case, a commercial freezer / refrigerator, an ice maker or a vending machine.

The heat cycle working medium of the present invention is nonflammable, has little influence on the ozone layer and global warming, has excellent cycle performance when used in a heat cycle system, and is excellent in safety.
The thermal cycle system of the present invention has a non-flammable working medium, has little influence on the ozone layer and global warming even if leaked, has excellent cycle performance, and is excellent in safety.

It is the schematic block diagram which showed the refrigerating cycle system which is an example of the thermal cycle system of this invention. FIG. 2 is a cycle diagram in which a change in state of a working medium in the refrigeration cycle system of FIG. 1 is described on a pressure-enthalpy diagram. FIG. 3 is a diagram showing a combustion range of HFO-1123 / HFC-134a / air system in Example 1. 6 is a diagram showing a combustion range of HFO-1123 / HFC-125 / air system in Example 2. FIG. FIG. 16 is a diagram showing a vapor-liquid equilibrium relationship of the HFO-1123 / HFC-134a system in Example 16. FIG. 18 is a view showing a vapor-liquid equilibrium relationship of HFO-1123 / HFC-125 system in Example 17.

[Working medium for thermal cycle]
The working medium for heat cycle (hereinafter, also simply referred to as working medium) of the present invention is a working medium containing HFO-1123 and one or both of HFC-134a and HFC-125. The working medium of the present invention preferably further comprises HFO-1234yf.

In the thermal cycle system using the working medium of the present invention, the combustibility of the working medium in the gas phase can be suppressed by controlling the ratio of the HFO-1123 in the gas phase formed in the system to a specific range. The present inventor found out.
In the present invention, “the gas phase formed in the system” means a working medium existing in the gas phase in the system. In the system, a part of the working medium may exist in a liquid state, and a part of the working medium may be dissolved in a coexisting liquid such as a lubricating oil. Therefore, the working medium in the gas phase formed in the system is a part excluding the working medium that is liquefied and the working medium that is dissolved in a liquid such as lubricating oil.

In the thermal cycle system of the present invention, the proportion of HFO-1123 in the gas phase formed in the system is 50% by mass or less.
The ratio of HFO-1123 in the gas phase formed in the system is 50% by mass or less means that the ratio of HFO-1123 in the gas phase formed in all processes of the system is always 50% by mass or less. It means that there is. When the proportion of HFO-1123 in the gas phase formed in the system is 50% by mass or less, the gas phase working medium leaks out of the system and is incombustible even when mixed with air, thus ensuring safety. Excellent.

The proportion of HFO-1123 in the gas phase formed in the system is 50% by mass or less, preferably 5 to 50% by mass, more preferably 10 to 45% by mass, and further preferably 10 to 40% by mass. If the ratio of HFO-1123 in the gas phase is less than or equal to the upper limit value, the working medium leaks out of the system and is nonflammable even when mixed with air, which is excellent in safety. When the ratio of HFO-1123 in the gas phase is equal to or higher than the lower limit, excellent cycle performance is easily obtained.
For the same reason, the ratio of HFO-1123 in the gas phase formed in the system in the case of the composition of HFO-1123 and HFC-134a is 50% by mass or less, preferably 5 to 40% by mass, 21 to 39% by mass is more preferable, and 21 to 30% by mass is even more preferable.
For the same reason, the ratio of HFO-1123 in the gas phase formed in the system in the case of the composition of HFO-1123 and HFC-125 is 50% by mass or less, preferably 5 to 50% by mass, 5 to 42% by mass is more preferable, and 21 to 39% by mass is more preferable.
For the same reason, the proportion of HFO-1123 in the gas phase formed in the system in the case of the composition of HFO-1123, HFC-134a and HFC-125 is not more than 50% by mass and is 5 to 50% by mass. %, More preferably 5 to 45% by mass, still more preferably 10 to 35% by mass.

The ratio of HFO-1123 to the total mass (100% by mass) of the working medium in the system of the thermal cycle system is preferably 42% by mass or less, more preferably 5 to 42% by mass, further preferably 10 to 35% by mass, 10 to 30% by mass is particularly preferable. When the ratio of HFO-1123 is equal to or higher than the lower limit, excellent cycle performance can be easily obtained. If the ratio of the HFO-1123 is less than or equal to the upper limit, the flammability of the gas phase working medium formed in the system is suppressed, so that the working medium leaks out of the system, mixes with air, and ignites. Even if it does not spread easily, it is excellent in safety.
The “total mass of the working medium in the system” means the total amount of the working medium present in the gas phase in the system, the working medium present in liquid form, and the working medium dissolved in the liquid such as lubricating oil, That is, the total amount of working medium present in the system. Thus, the ratio of each working medium component (eg, HFO-1123) to the total working medium mass in the system is equal to the ratio of each working medium component in the working medium.

The ratio of the total amount of HFC-134a and HFC-125 to the total mass of the working medium in the system is preferably 58% by mass or more, more preferably 58 to 95% by mass, further preferably 65 to 90% by mass, ˜90% by weight is most preferred. When the ratio of the total mass is equal to or more than the lower limit value, it is easy to suppress the combustibility of the gas phase working medium formed in the system. If the ratio of the total mass is equal to or less than the upper limit value, the content of HFO-1123 can be relatively increased, so that excellent cycle performance can be easily obtained.

The working medium of the present invention includes HFO-1123, HFC-134a, HFC-125, and HFO-1234yf, and the total amount of HFO-1123, HFC-134a, HFC-125, and HFO-1234yf with respect to the total amount of the working medium. The ratio is more than 90% by mass and 100% by mass or less, and the ratio of HFO-1123 to the total amount of HFO-1123, HFC-134a, HFC-125, and HFO-1234yf is 3% by mass to 35% by mass, The ratio of HFC-134a is preferably 10% by mass to 53% by mass, the ratio of HFC-125 is 4% by mass to 50% by mass, and the ratio of HFO-1234yf is preferably 5% by mass to 50% by mass. By using such a working medium, the working medium is non-flammable and excellent in safety, has less influence on the ozone layer and global warming, and has better cycle performance when used in a thermal cycle system. It can be set as the working medium which has these.

Furthermore, the working medium of the present invention includes HFO-1123, HFC-134a, HFC-125, and HFO-1234yf, and the total of HFO-1123, HFC-134a, HFC-125, and HFO-1234yf with respect to the total amount of the working medium. The ratio of the amount is more than 90% by mass and not more than 100% by mass, and the ratio of HFO-1123 to the total amount of HFO-1123, HFC-134a, HFC-125, and HFO-1234yf is 6% by mass or more and 25% by mass Hereinafter, the ratio of HFC-134a is 20% by mass to 35% by mass, the ratio of HFC-125 is 8% by mass to 30% by mass, and the ratio of HFO-1234yf is 20% by mass to 50% by mass. Even more preferred. By using such a working medium, the working medium is non-flammable, and is more excellent in safety, has less influence on the ozone layer and global warming, and is even better when used in a heat cycle system. The working medium having a high cycle performance can be obtained.

As long as the working medium does not impair the effects of the present invention, HFO other than HFO-1123 and HFO-1234yf, HFC other than HFC-134a and HFC-125, hydrocarbon, HCFO, CFO, It may contain other compounds.

(HFO other than HFO-1123 and HFO-1234yf)
Examples of HFO other than HFO-1123 and HFO-1234yf include 1,2-difluoroethylene (HFO-1132), 2-fluoropropene (HFO-1261yf), 1,1,2-trifluoropropene (HFO-1243yc), Trans-1,3,3,3-tetrafluoropropene (HFO-1234ze (E)), cis-1,3,3,3-tetrafluoropropene (HFO-1234ze (Z)), 3,3,3- Trifluoropropene (HFO-1243zf), trans-1,2,3,3,3-pentafluoropropene (HFO-1225ye (E)), cis-1,2,3,3,3-pentafluoropropene (HFO) -1225ye (Z)) and the like.
HFOs other than HFO-1123 and HFO-1234yf may be used alone or in combination of two or more.

When the working medium contains HFO other than HFO-1123 and HFO-1234yf, the ratio of the total mass of the HFO to the total mass (100% by mass) of the working medium in the system is preferably 1 to 30% by mass. 10 mass% is more preferable.

(HFC other than HFC-134a and HFC-125)
HFCs other than HFC-134a and HFC-125 are components that improve the cycle performance (capability) of the thermal cycle system. As HFCs other than HFC-134a and HFC-125, HFCs that have little influence on the ozone layer and little influence on global warming are preferable.

Examples of HFCs other than HFC-134a and HFC-125 include difluoromethane, difluoroethane, trifluoroethane, pentafluoropropane, hexafluoropropane, heptafluoropropane, pentafluorobutane, heptafluorocyclopentane, and the like. Of these, difluoromethane (HFC-32) and 1,1-difluoroethane (HFC-152a) are particularly preferable because they have little influence on the ozone layer and little influence on global warming.
HFCs other than HFC-134a and HFC-125 may be used alone or in combination of two or more.

The content of HFC other than HFC-134a and HFC-125 can be controlled according to the required characteristics of the working medium.
When the working medium contains HFCs other than HFC-134a and HFC-125, the ratio of the total mass of the HFC to the total mass (100% by mass) of the working medium in the system is preferably 1 to 40% by mass. 10 mass% is more preferable.

(hydrocarbon)
A hydrocarbon is a component which improves the solubility to the working medium of the mineral oil mentioned later.
Examples of the hydrocarbon include propane, propylene, cyclopropane, butane, isobutane, pentane, isopentane and the like.
A hydrocarbon may be used individually by 1 type and may be used in combination of 2 or more type.

When the working medium contains hydrocarbons, the ratio of the total mass of hydrocarbons to the total mass (100% by mass) of the working medium in the system is preferably 1 to 10% by mass, and more preferably 2 to 5% by mass. If the ratio of the total mass of the hydrocarbon is not less than the lower limit value, the solubility of the lubricating oil in the working medium becomes good. If the ratio of the total mass of the hydrocarbon is equal to or less than the upper limit value, it is easy to suppress the combustibility of the working medium.

(HCFO, CFO)
HCFO and CFO are components that suppress the combustibility of the working medium and improve the solubility of the lubricating oil in the working medium. As HCFO and CFO, HCFO and CFO having a small influence on the ozone layer and a small influence on global warming are preferable.

Examples of HCFO include hydrochlorofluoropropene and hydrochlorofluoroethylene. Among them, 1-chloro-2,3,3,3-tetrafluoropropene (HCFO-) is preferable because it does not significantly reduce the cycle performance (capacity) of the thermal cycle system, and the flammability of the working medium can be sufficiently suppressed. 1224yd), 1-chloro-1,2-difluoroethylene (HCFO-1122).
HCFO may be used alone or in combination of two or more.

Examples of CFO include chlorofluoropropene and chlorofluoroethylene. In particular, 1,1-dichloro-2,3,3,3-tetrafluoropropene (CFO) is used from the viewpoint of sufficiently suppressing the flammability of the working medium without greatly reducing the cycle performance (capacity) of the thermal cycle system. -1214ya), 1,2-dichloro-1,2-difluoroethylene (CFO-1112).

When the working medium includes one or both of HCFO and CFO, the ratio of the total mass of HCFO and CFO to the total mass (100 mass%) of the working medium in the system is preferably 1 to 20 mass%. More preferred is 10% by mass. Chlorine atoms have the effect of suppressing flammability, and the addition of HCFO and CFO can sufficiently suppress the flammability of the working medium without significantly reducing the cycle performance (capability) of the thermal cycle system. .

(Other compounds)
Examples of other compounds include alcohols having 1 to 4 carbon atoms, or compounds used as conventional working media, refrigerants, and heat transfer media. Also, perfluoropropyl methyl ether (C ₃ F ₇ OCH ₃ ), perfluorobutyl methyl ether (C ₄ F ₉ OCH ₃ ), perfluorobutyl ethyl ether (C ₄ F ₉ OC ₂ H ₅ ), 1, 1, _{2, 2} Fluorine-containing ethers such as tetrafluoroethyl-2,2,2-trifluoroethyl ether (CF ₂ HCF ₂ OCH ₂ CF ₃ , manufactured by Asahi Glass Co., Ltd., AE-3000) may be used.

The ratio of the total mass of other compounds to the total mass (100 mass%) of the working medium in the system may be in a range that does not significantly reduce the effect of the present invention, preferably 30 mass% or less, and preferably 20 mass% or less. More preferred is 15% by mass or less.

[Application to thermal cycle system]
<Composition for thermal cycle system>
The working medium of the present invention can be used as a composition for a heat cycle system, usually mixed with a lubricating oil when applied to a heat cycle system. In addition to these, the composition for a heat cycle system containing the working medium and the lubricating oil of the present invention may further contain known additives such as a stabilizer and a leak detection substance.

[Lubricant]
In the thermal cycle system of the present invention, the working medium described above may be used by mixing with a lubricating oil. As the lubricating oil, a known lubricating oil used in a heat cycle system can be employed.
Examples of the lubricating oil include oxygen-containing synthetic oils (such as ester-based lubricating oils and ether-based lubricating oils), fluorine-based lubricating oils, mineral oils, and hydrocarbon-based synthetic oils.

Examples of the ester-based lubricating oil include dibasic acid ester oil, polyol ester oil, complex ester oil, and polyol carbonate oil.
The dibasic acid ester oil includes a dibasic acid having 5 to 10 carbon atoms (glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, etc.) and a carbon number having a linear or branched alkyl group. Esters with 1 to 15 monohydric alcohols (methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, etc.) are preferred. Specific examples include ditridecyl glutarate, di (2-ethylhexyl) adipate, diisodecyl adipate, ditridecyl adipate, di (3-ethylhexyl) sebacate and the like.

Polyol ester oils include diols (ethylene glycol, 1,3-propanediol, propylene glycol, 1,4-butanediol, 1,2-butanediol, 1,5-pentadiol, neopentyl glycol, 1,7- Heptanediol, 1,12-dodecanediol, etc.) or polyol having 3 to 20 hydroxyl groups (trimethylolethane, trimethylolpropane, trimethylolbutane, pentaerythritol, glycerin, sorbitol, sorbitan, sorbitol glycerin condensate, etc.); Fatty acids having 6 to 20 carbon atoms (hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid, eicosanoic acid, oleic acid and other straight chain or branched fatty acids, or 4 carbon atoms. So-called neo Etc.), esters of is preferable.
The polyol ester oil may have a free hydroxyl group.
Polyol ester oils include esters of hindered alcohols (neopentyl glycol, trimethylol ethane, trimethylol propane, trimethylol butane, pentaerythritol, etc.) (trimethylol propane tripelargonate, pentaerythritol 2-ethylhexanoate). And pentaerythritol tetrapelargonate) are more preferable.

The complex ester oil is an ester of a fatty acid and a dibasic acid, a monohydric alcohol and a polyol. Examples of the fatty acid, dibasic acid, monohydric alcohol, and polyol include the same as those mentioned for the dibasic acid ester oil and polyol ester oil.

The polyol carbonate oil is an ester of carbonic acid and polyol.
Examples of the polyol include diols and polyols (same as those mentioned for the polyol ester oil). Further, the polyol carbonate oil may be a ring-opening polymer of cyclic alkylene carbonate.

Examples of ether lubricants include polyoxyalkylene compounds and polyvinyl ethers.
Examples of the polyoxyalkylene compound include polyoxyalkylene compounds obtained by polymerizing alkylene oxides having 2 to 4 carbon atoms (ethylene oxide, propylene oxide, etc.) using water, alkane monool, the diol, the polyol, or the like as an initiator. Examples include alkylene monools and polyoxyalkylene polyols. As the polyoxyalkylene compound, a part or all of the hydroxyl groups of polyoxyalkylene monool or polyoxyalkylene polyol may be alkyl etherified.
The number of oxyalkylene units in one molecule of the polyoxyalkylene compound may be one, or two or more. As the polyoxyalkylene compound, those containing at least an oxypropylene unit in one molecule are preferable.

Polyalkylene glycol oil is one of the above polyoxyalkylene compounds, and examples thereof include the above polyoxyalkylene monools, polyoxyalkylene diols, and alkyl etherified products thereof. Specifically, for example, a polyhydride obtained by adding an alkylene oxide having 2 to 4 carbon atoms to a monohydric or dihydric alcohol (methanol, ethanol, butanol, ethylene glycol, propylene glycol, 1,4-butanediol, etc.). Examples include oxyalkylene compounds and compounds obtained by alkyl etherifying some or all of the hydroxyl groups of the obtained polyoxyalkylene compounds.
The polyalkylene glycol oil is preferably a dialkyl ether of polyoxypropylene diol.

Examples of the polyvinyl ether include a polymer of a vinyl ether monomer, a copolymer of a vinyl ether monomer and a hydrocarbon monomer having an olefinic double bond, and a copolymer of a vinyl ether monomer and a vinyl ether monomer having a polyoxyalkylene chain. It is done.
The vinyl ether monomer is preferably an alkyl vinyl ether, and the alkyl group is preferably an alkyl group having 6 or less carbon atoms. Moreover, a vinyl ether monomer may be used individually by 1 type, and may be used in combination of 2 or more type.
Examples of hydrocarbon monomers having an olefinic double bond include ethylene, propylene, various butenes, various pentenes, various hexenes, various heptenes, various octenes, diisobutylene, triisobutylene, styrene, α-methylstyrene, various alkyl-substituted styrenes, etc. Is mentioned. The hydrocarbon monomer which has an olefinic double bond may be used individually by 1 type, and may be used in combination of 2 or more type.
The vinyl ether copolymer may be either a block or a random copolymer.

Examples of fluorine-based lubricating oils include compounds in which hydrogen atoms of synthetic oils (described later, such as mineral oils, poly α-olefins, alkylbenzenes, and alkylnaphthalenes) are substituted with fluorine atoms, perfluoropolyether oils, fluorinated silicone oils, and the like. .

As mineral oil, a lubricating oil fraction obtained by subjecting crude oil to atmospheric distillation or vacuum distillation is refined (solvent removal, solvent extraction, hydrocracking, solvent dewaxing, catalytic dewaxing, hydrorefining, hydrorefining, And paraffinic mineral oils, naphthenic mineral oils, etc., which are refined by appropriately combining white clay treatment and the like.

Examples of the hydrocarbon synthetic oil include poly α-olefin, alkylbenzene, alkylnaphthalene and the like.

A lubricating oil may be used individually by 1 type, and may be used in combination of 2 or more type.
As the lubricating oil, one or both of a polyol ester oil and a polyalkylene glycol oil are preferable from the viewpoint of compatibility with the working medium, and a polyalkylene glycol is preferable because a remarkable antioxidant effect is obtained by the stabilizer. Oil is particularly preferred.

When the working medium and the lubricating oil are mixed and used, the amount of the lubricating oil used may be in a range that does not significantly reduce the effect of the present invention, and may be appropriately determined depending on the application, the type of the compressor, and the like. The ratio of the total mass of the lubricating oil in the system is preferably 10 to 100 parts by mass and more preferably 20 to 50 parts by mass with respect to 100 parts by mass of the working medium.

[Stabilizer]
A stabilizer is a component that improves the stability of the working medium against heat and oxidation. Examples of the stabilizer include an oxidation resistance improver, a heat resistance improver, and a metal deactivator.
Examples of the oxidation resistance improver and heat resistance improver include N, N′-diphenylphenylenediamine, p-octyldiphenylamine, p, p′-dioctyldiphenylamine, N-phenyl-1-naphthylamine, and N-phenyl-2-naphthylamine. N- (p-dodecyl) phenyl-2-naphthylamine, di-1-naphthylamine, di-2-naphthylamine, N-alkylphenothiazine, 6- (t-butyl) phenol, 2,6-di- (t-butyl) ) Phenol, 4-methyl-2,6-di- (t-butyl) phenol, 4,4′-methylenebis (2,6-di-t-butylphenol) and the like. The oxidation resistance improver and the heat resistance improver may be used alone or in combination of two or more.

Metal deactivators include imidazole, benzimidazole, 2-mercaptobenzthiazole, 2,5-dimercaptothiadiazole, salicyridin-propylenediamine, pyrazole, benzotriazole, tolyltriazole, 2-methylbenzimidazole, 3,5-dimethyl Of pyrazole, methylenebis-benzotriazole, organic acids or their esters, primary, secondary or tertiary aliphatic amines, amine salts of organic or inorganic acids, heterocyclic nitrogen-containing compounds, alkyl acid phosphates Examples thereof include amine salts and derivatives thereof.

The ratio of the total mass of the stabilizer to the total mass (100 mass%) of the working medium in the system may be in a range that does not significantly reduce the effect of the present invention, preferably 5 mass% or less, and more preferably 1 mass% or less. preferable.

[Leak detection substance]
Examples of leak detection substances include ultraviolet fluorescent dyes, odorous gases and odor masking agents.
The ultraviolet fluorescent dyes are described in U.S. Pat. No. 4,249,412, JP-T-10-502737, JP-T 2007-511645, JP-T 2008-500437, JP-T 2008-531836. And known ultraviolet fluorescent dyes.
Examples of the odor masking agent include known fragrances such as those described in JP-T-2008-500337 and JP-T-2008-531836.

In the case of using a leak detection substance, a solubilizing agent that improves the solubility of the leak detection substance in the working medium may be used.
Examples of the solubilizer include those described in JP-T-2007-511645, JP-T-2008-500437, JP-T-2008-531836.

The ratio of the total mass of the leakage detection substance to the total mass (100 mass%) of the working medium in the system may be in a range that does not significantly reduce the effect of the present invention, and is preferably 2 mass% or less, preferably 0.5 mass%. The following is more preferable.

[Moisture concentration]
For example, in an air conditioner for an automobile, moisture tends to easily enter from a refrigerant hose or a bearing portion of a compressor used for absorbing vibration.
When moisture is mixed in the thermal cycle system, problems such as freezing in the capillary tube, hydrolysis of the working medium and lubricating oil, material deterioration due to acid components generated in the system, and generation of contamination occur. In particular, polyalkylene glycol oil, polyol ester oil, etc. have extremely high hygroscopicity, are prone to hydrolysis reaction, and the properties as a lubricating oil are reduced. When mixed with water, the long-term reliability of the compressor is impaired. Cause. Therefore, in order to suppress hydrolysis of the lubricating oil, it is necessary to suppress the moisture concentration in the heat cycle system.

As a method for suppressing the water concentration in the heat cycle system, a method using a desiccant (silica gel, activated alumina, zeolite, etc.) can be mentioned. As the desiccant, a zeolitic desiccant is preferable from the viewpoint of the chemical reactivity between the desiccant and the working medium and the moisture absorption capacity of the desiccant.

As a zeolitic desiccant, when a lubricating oil having a higher moisture absorption than conventional mineral oils is used, a zeolitic system mainly composed of a compound represented by the following formula (1) is used because of its superior moisture absorption capacity. A desiccant is preferred.
_{M 2 / n O · Al 2} O 3 · xSiO 2 · yH 2 O ··· (1).
Here, M is a Group 1 element such as Na or K, or a Group 2 element such as Ca, n is the valence of M, and x and y are values determined by the crystal structure. By changing M, the pore diameter can be adjusted.

In selecting a desiccant, pore size and fracture strength are particularly important.
When a desiccant having a pore size larger than the molecular diameter of the working medium is used, the working medium is adsorbed in the desiccant, resulting in a chemical reaction between the working medium and the desiccant, and generation of a non-condensable gas. Undesirable phenomena such as a decrease in the strength of the desiccant and a decrease in the adsorption capacity will occur.
Therefore, it is preferable to use a zeolitic desiccant having a small pore size as the desiccant. In particular, a sodium / potassium A type synthetic zeolite having a pore diameter of 3.5 mm or less is preferable. By applying sodium / potassium type A synthetic zeolite having a pore diameter smaller than the molecular diameter of the working medium, only moisture in the thermal cycle system can be selectively adsorbed and removed without adsorbing the working medium. Since adsorption of the working medium to the desiccant is unlikely to occur, thermal decomposition of the working medium is unlikely to occur, and as a result, it is possible to suppress deterioration of materials constituting the thermal cycle system and generation of contamination.

If the size of the zeolitic desiccant is too small, it will cause clogging of the expansion valve and piping details of the heat cycle system, and if it is too large, the drying ability will be reduced, so about 0.5 to 5 mm is preferable. The shape of the zeolitic desiccant is preferably granular or cylindrical.
The zeolitic desiccant can be formed into an arbitrary shape by solidifying powdered zeolite with a binder (such as bentonite). As long as the zeolitic desiccant is mainly used, other desiccants (silica gel, activated alumina, etc.) may be used in combination.
The use ratio of the zeolitic desiccant with respect to the working medium is not particularly limited.

[Chlorine concentration]
The presence of chlorine in the thermal cycle system has adverse effects such as deposit formation due to reaction with metal, bearing wear, decomposition of working medium and lubricating oil.
The chlorine concentration in the heat cycle system is preferably 100 ppm or less, and particularly preferably 50 ppm or less in terms of a mass ratio with respect to the working medium.

[Noncondensable gas concentration]
If a non-condensable gas is mixed in the heat cycle system, adverse effects such as poor heat transfer in the condenser or evaporator and an increase in operating pressure are required, so it is necessary to suppress the mixing of the non-condensable gas as much as possible. In particular, oxygen, which is one of non-condensable gases, reacts with the working medium and lubricating oil and promotes its decomposition. Non-condensable gases include nitrogen, oxygen, air and the like.
The concentration of the non-condensable gas in the thermal cycle system is preferably 1.5% by volume or less, particularly preferably 0.5% by volume or less, in the volume ratio with respect to the working medium in the gas phase in the system.

Examples of the heat cycle system of the present invention include a refrigeration cycle system, a Rankine cycle system, a heat pump cycle system, and a heat transport system.

[Refrigeration cycle system]
The refrigeration cycle system is a system that cools the load fluid to a lower temperature by removing the heat energy from the load fluid in the evaporator in the evaporator.
Hereinafter, a specific example of the refrigeration cycle system will be described with reference to FIG.
The refrigeration cycle system 10 compresses the working medium vapor A into a high-temperature and high-pressure working medium vapor B, and cools and liquefies the working medium vapor B discharged from the compressor 11 to operate at a low temperature and high pressure. The condenser 12 as the medium C, the expansion valve 13 that expands the working medium C discharged from the condenser 12 to form the low-temperature and low-pressure working medium D, and the working medium D discharged from the expansion valve 13 are heated. A system schematically including an evaporator 14 that is a high-temperature and low-pressure working medium vapor A, a pump 15 that supplies a load fluid E to the evaporator 14, and a pump 16 that supplies a fluid F to the condenser 12. is there.

In the refrigeration cycle system 10, the following cycle is repeated.
(I) The working medium vapor A discharged from the evaporator 14 is compressed by the compressor 11 to obtain a high-temperature and high-pressure working medium vapor B.
(Ii) The working medium vapor B discharged from the compressor 11 is cooled by the fluid F in the condenser 12 and liquefied to obtain a low temperature and high pressure working medium C. At this time, the fluid F is heated to become a fluid F ′ and discharged from the condenser 12.
(Iii) The working medium C discharged from the condenser 12 is expanded by the expansion valve 13 to obtain a low-temperature and low-pressure working medium D.
(Iv) The working medium D discharged from the expansion valve 13 is heated by the load fluid E in the evaporator 14 to obtain high-temperature and low-pressure working medium vapor A. At this time, the load fluid E is cooled to become a load fluid E ′ and is discharged from the evaporator 14.

The refrigeration cycle system 10 is a cycle composed of adiabatic / isentropic change, isenthalpy change and isobaric change, and the state change of the working medium can be expressed as shown in FIG. 2 on the pressure-enthalpy diagram.
In FIG. 2, the AB process is a process in which adiabatic compression is performed by the compressor 11 and the high-temperature and low-pressure working medium vapor A is converted into a high-temperature and high-pressure working medium vapor B. The BC process is a process in which isobaric cooling is performed by the condenser 12 and the high-temperature and high-pressure working medium vapor B is converted into a low-temperature and high-pressure working medium C. The CD process is a process in which isenthalpy expansion is performed by the expansion valve 13 and the low-temperature and high-pressure working medium C is used as the low-temperature and low-pressure working medium D. The DA process is a process in which isobaric heating is performed by the evaporator 14 and the low-temperature and low-pressure working medium D is returned to the high-temperature and low-pressure working medium vapor A.

[Rankin cycle system]
In the Rankine cycle system, the working medium is heated in the evaporator by geothermal energy, solar heat, medium to high temperature waste heat of about 50 to 200 ° C, etc., and the working medium turned into high-temperature and high-pressure steam is insulated by an expander. This is a system for generating power by driving the generator by work generated by expansion and adiabatic expansion.

Specific examples of the Rankine cycle system include the following.
An expander that expands high-temperature and high-pressure working medium vapor into low-temperature and low-pressure working medium vapor, a generator driven by work generated by adiabatic expansion of the working medium vapor in the expander, and operation discharged from the expander A condenser that cools and vaporizes the medium vapor to form a working medium, a pump that pressurizes the working medium discharged from the condenser to form a high-pressure working medium, and heats the working medium discharged from the pump to a high temperature A system that includes an evaporator configured as high-pressure working medium vapor, a pump that supplies fluid to the condenser, and a pump that supplies fluid to the evaporator.

In the Rankine cycle system, the following cycle is repeated.
(I) The high-temperature and high-pressure working medium vapor discharged from the evaporator is expanded by an expander to form a low-temperature and low-pressure working medium vapor. At this time, the generator is driven by work generated by adiabatic expansion of the working medium vapor in the expander to generate power.
(Ii) The working medium vapor discharged from the expander is cooled with a fluid in a condenser and liquefied to form a working medium. At this time, the fluid supplied to the condenser is heated and discharged from the condenser.
(Iii) The working medium discharged from the condenser is pressurized with a pump to form a high-pressure working medium.
(Iv) The working medium discharged from the pump is heated by a fluid in an evaporator to form high-temperature and high-pressure working medium vapor. At this time, the fluid supplied to the evaporator is cooled and discharged from the evaporator.

[Heat pump cycle system]
The heat pump cycle system is a system in which heat energy of a working medium is given to a load fluid in a condenser to heat the load fluid and raise the temperature to a higher temperature.

Specific examples of the heat pump cycle system include the following.
A compressor that compresses the working medium vapor into a high-temperature and high-pressure working medium vapor, a condenser that cools and liquefies the working medium vapor discharged from the compressor, and discharges it from the condenser Expansion valve that expands the working medium into a low-temperature and low-pressure working medium, an evaporator that heats the working medium discharged from the expansion valve into high-temperature and low-pressure working medium vapor, and supplies a heat source fluid to the evaporator And a pump that supplies a load fluid to the condenser.

In the heat pump cycle system, the following cycle is repeated.
(I) The working medium vapor discharged from the evaporator is compressed by a compressor to form a high-temperature and high-pressure working medium vapor.
(Ii) The working medium vapor discharged from the compressor is cooled by a load fluid in a condenser and liquefied to obtain a low temperature and high pressure working medium. At this time, the load fluid is heated and discharged from the condenser.
(Iii) The working medium discharged from the condenser is expanded by an expansion valve to form a low-temperature and low-pressure working medium.
(Iv) The working medium discharged from the expansion valve is heated by a heat source fluid in an evaporator to form high-temperature and low-pressure working medium vapor. At this time, the heat source fluid is cooled and discharged from the evaporator.

[Heat transport system]
The heat transport system evaporates the working medium by a heat source and absorbs the heat energy in the working medium, transports the working medium in the form of vapor, condenses it at the destination, releases the heat energy, and transports the heat energy. System.

Specific examples of the heat transport system include the following.
A pipe disposed from a heat source to a heat transport destination, in which a working medium is enclosed, a wig (mesh structure) disposed on the inner surface of the pipe, and an end of the pipe opposite to the heat source. A system that includes a heat dissipating section and is generally configured.

In the heat transport system, the following cycle is repeated.
(I) In the pipe on the heat source side, the working medium is evaporated by the heat energy from the heat source to form working medium vapor.
(Ii) The working medium vapor is transported from the heat source side to the heat radiating portion, and the working medium vapor is condensed and liquefied in the heat radiating portion.
(Iii) The liquefied working medium is transported by the wig to the heat source side using the capillary action and circulated.

[Usage]
Applications of the thermal cycle system include, for example, refrigeration / refrigeration equipment, air conditioning equipment, power generation systems, heat transport devices, or secondary coolers.
More specifically, for example, room air conditioners, store packaged air conditioners, building packaged air conditioners, facility packaged air conditioners, gas engine heat pumps, train air conditioners, automotive air conditioners, built-in showcases, separate showcases, Commercial freezer / refrigerator, ice machine or vending machine.

[Global warming potential (GWP)]
In the present invention, GWP is used as an index for measuring the influence of the working medium on global warming. In this specification, unless otherwise specified, GWP is the value of 100 in the Intergovernmental Panel on Climate Change (IPCC) Fourth Assessment Report (2007).
Table 1 shows the GWP of each compound.

The global warming potential (100 years) of HFO-1123 contained in the working medium according to the present invention is 0.3. This value is much smaller than GWP of other HFOs, for example, 6 of HFO-1234ze, 4 of HFO-1234yf, and the like.

In addition, R410A (HFC-125 and HFC-32 used in air conditioning applications such as room air conditioners, store packaged air conditioners, building packaged air conditioners, and facility packaged air conditioners to be replaced by the working medium according to the present invention. 1: 1 (mass) composition) has a very high GWP of 2088. Also, R404A (HFC-125 and 1,1,1-trifluoroethane (HFC-143a) and HFC, which are used for freezing and refrigeration applications such as built-in showcases, stand-alone showcases, and commercial refrigeration / refrigerators. The 11: 13: 1 (mass) composition with -134a) has a GWP that is twice as large as 3922 and R410A.

The working medium of the present invention preferably has a low global warming potential from the viewpoint of the effect on global warming. Specifically, the GWP of the working medium of the present invention is preferably 2000 or less, more preferably 1500 or less, and particularly preferably 1000 or less. GWP2000 is about 50% of R404A used for freezing and refrigeration applications, GWP1000 is about 25% of R404A and about 50% of R410A used for air conditioning applications. It shows that the influence can be reduced.
The GWP in the mixture is a weighted average based on the composition mass. For example, the GWP in a 1: 1 mass ratio mixture of HFO-1123 and HFC-134a can be calculated as (0.3 + 1430) / 2 = 715. When the working medium of the present invention contains optional components other than HFO-1123, HFC-134a, and HFC-125, the GWP per unit mass of the optional component is further weighted averaged by the composition mass, The GWP of the working medium can be obtained.

[Function and effect]
In the heat cycle system of the present invention described above, since the working medium containing HFO-1123 and one or both of HFC-134a and HFC-125 is used, the influence on the ozone layer and global warming is reduced. Few.
The thermal cycle system of the present invention is also excellent in cycle performance.
Further, since the ratio of HFO-1123 in the gas phase formed in the system is controlled to be 50% by mass or less, the combustibility of the gas phase working medium can be suppressed. Therefore, if the working medium in the gas phase in the system leaks, mixes with air, and does not spread easily even when ignited, safety is ensured.

EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited by the following description.
[Evaluation of flammability]
The evaluation of flammability was carried out using equipment specified in ASTM E-681.
After evacuating the flask with an internal volume of 12 liters installed in a thermostat controlled at 25 ° C., the working medium and air adjusted to the respective concentrations plotted in FIG. 3 or FIG. 4 were sealed up to atmospheric pressure. . Thereafter, in the gas phase in the vicinity of the center in the flask, discharge ignition was performed at 15 kV and 30 mA for 0.4 seconds, and then the spread of the flame was visually confirmed. The case where the upward flame spread angle exceeded 90 ° was judged as combustible, and the case where it was less than 90 ° was judged as non-combustible.

[Example 1]
HFO-1123 and HFC-134a were mixed at a predetermined ratio to evaluate the combustibility of the two-component working medium. FIG. 3 shows the relationship between the proportion of HFO-1123, HFC-134a and air in the gas phase in the flask and the combustibility.

As shown in FIG. 3, the proportion of HFO-1123 in the working medium in the gas phase in the flask is 50% by mass or less (on the right side of the straight line indicating HFO-1123: HFC-134a = 1: 1 in FIG. 3). ) Was found not to have a combustion range (a range in which “combustibility” occurs). In other words, the working medium having a HFO-1123 ratio of 50 mass% or less in the working medium in the gas phase can be suppressed in combustibility regardless of the concentration of the working medium in the gas phase with air. all right.

[Example 2]
HFO-1123 and HFC-125 were mixed at a predetermined ratio to evaluate the combustibility of the two-component working medium. FIG. 4 shows the relationship between the proportion of HFO-1123, HFC-125 and air in the gas phase in the flask and the presence or absence of combustibility.

As shown in FIG. 4, the proportion of HFO-1123 in the working medium in the gas phase in the flask is 50% by mass or less (on the right side of the straight line indicating HFO-1123: HFC-125 = 1: 1 in FIG. 4). ) Was found not to have a combustion range (a range in which “combustibility” occurs). In other words, the working medium having a HFO-1123 ratio of 50 mass% or less in the working medium in the gas phase can be suppressed in combustibility regardless of the concentration of the working medium in the gas phase with air. all right.

[Examples 3 to 7]
HFO-1123, HFC-134a, and HFC-125 are mixed so that the ratio of each medium in the gas phase when reaching the equilibrium state is as shown in Table 2 to prepare a three-component working medium Then, the combustibility was evaluated when the working medium was mixed with air at a ratio of every 10% by mass between 10 to 90% by mass with respect to the air to reach an equilibrium state.
The evaluation results are shown in Table 2.

As shown in Table 2, the working media of Examples 3 to 6 in which the ratio of HFO-1123 in the working fluid in the gas phase in the flask was 50% by mass or less were suppressed in combustibility.
On the other hand, in Example 7 in which the proportion of HFO-1123 in the working medium in the gas phase in the flask was more than 50% by mass, the combustibility could not be suppressed.

[Examples 8 to 12]
A pressure-resistant container having an internal volume of 12 liters was charged with 9 kg of a three-component working medium in which HFO-1123, HFC-134a, and HFC-125 were mixed at the ratio shown in Table 3.
After reaching the equilibrium state, a gas phase working medium was collected from the pressure vessel, and the working medium was mixed with air at an arbitrary ratio in the flask, and the flammability was evaluated in the same manner as in Examples 1-7.

As shown in Table 3, in Examples 8 to 10 in which the ratio of the total mass of HFO-1123 to the total mass of the working medium in the pressure vessel is 42% by mass or less, the vapor-phase working medium that has reached the equilibrium state has any concentration. The flammability was suppressed even when mixed with air. This is because the proportion of HFO-1123 in the gas phase that has reached an equilibrium state is 50 mass% or less.
On the other hand, in Examples 11 and 12 in which the ratio of the total mass of HFO-1123 to the total mass of the working medium in the pressure vessel was 50% by mass, the combustibility of the vapor-phase working medium that reached the equilibrium state could not be suppressed. This is because in Examples 11 and 12, HFO-1123 is more easily volatilized than HFC-134a and HFC-125, so the proportion of HFO-1123 in the gas phase that has reached an equilibrium state exceeds 50% by mass. It is.

[Examples 13 to 15]
HFO-1123, HFC-134a, HFC-125, and HFO-1234yf are mixed so that the ratio of each medium in the gas phase when the equilibrium state is reached is as shown in Table 4 to operate a four-component system A medium was prepared, and the flammability when the working medium was mixed with air at a ratio of every 10% by mass between 10 to 90% by mass with respect to air to reach an equilibrium state was evaluated.
The evaluation results are shown in Table 4.
As shown in Table 4, the working media of Examples 13 to 15 were suppressed in combustibility.

For the working medium containing HFO-1123 and one or both of HFC-134a and HFC-125, the gas-liquid equilibrium state relationship was evaluated as follows.

[Example 16]
(Evaluation of vapor-liquid equilibrium relationship)
HFO-1123 and HFC-134a having predetermined concentrations were filled in a pressure-resistant container at 25 ° C., stirred, and allowed to stand until a vapor-liquid equilibrium state was reached. Thereafter, the gas phase and the liquid phase in the pressure vessel were collected, and the composition was analyzed by gas chromatography. The results are shown in FIG.
FIG. 5 shows the liquid phase concentration (mass%) and gas phase concentration (mass%) of HFO-1123 in a vapor-liquid equilibrium state of a mixture composed of HFO-1123 and HFC-134a prepared by changing the above various compositions. It is a graph which shows a relationship. In FIG. 5, the solid line shows the relationship between the liquid phase concentration (mass%) and gas phase concentration (mass%) of HFO-1123 measured above. FIG. 5 shows that when the concentration of HFO-1123 in the liquid phase in the vapor-liquid equilibrium state is 30% by mass, the concentration of HFO-1123 in the gas phase is 50% by mass. This confirms that it is nonflammable. On the other hand, when the concentration of HFO-1123 in the liquid phase in the vapor-liquid equilibrium state is 50% by mass, it indicates that the concentration of HFO-1123 in the gas phase is 67% by mass. It can be seen that it has a combustion range. In other words, a composition having a liquid phase concentration of 30% by mass or less of HFO-1123 in a vapor-liquid equilibrium state has an HFO-1123 concentration of 50% by mass or less in the gas phase in the sealed container, and is incombustible even in the gas phase. It is. Therefore, even when it leaks from the gas phase part by mistake or when the equipment is filled from the gas phase part, it does not have combustibility.

[Example 17]
The results obtained for HFO-1123 and HFC-125 in the same manner as in Example 16 are shown in FIG.
FIG. 6 shows the liquid phase concentration (mass%) and gas phase concentration (mass%) of HFO-1123 in a gas-liquid equilibrium state of a mixture consisting of HFO-1123 and HFC-125 prepared by changing the above various compositions. It is a graph which shows a relationship. FIG. 6 shows that when the concentration of HFO-1123 in the liquid phase in the vapor-liquid equilibrium state is 42% by mass, the concentration of HFO-1123 in the gas phase is 50% by mass. This confirms that it is nonflammable. On the other hand, when the concentration of HFO-1123 in the liquid phase in the vapor-liquid equilibrium state is 50% by mass, it indicates that the concentration of HFO-1123 in the gas phase is 68% by mass. It can be seen that it has a combustion range. In other words, a composition having a liquid phase concentration of 42% by mass or less of HFO-1123 in a vapor-liquid equilibrium state has an HFO-1123 concentration of 50% by mass or less in the gas phase portion in the sealed container, and is incombustible even in the gas phase. It is. Therefore, even when leaked from the gas phase part of the container or when it is accidentally filled into the equipment from the gas phase part, it has a feature of extremely high safety because it does not have combustibility.

[Evaluation of refrigeration cycle performance]
The refrigeration cycle performance (refrigeration capacity and coefficient of performance) was evaluated as the cycle performance (capacity and efficiency) when the working medium was applied to the refrigeration cycle system 10 of FIG.
In the evaluation, the average evaporation temperature of the working medium in the evaporator 14 is 0 ° C., the average condensation temperature of the working medium in the condenser 12 is 40 ° C., the degree of supercooling of the working medium in the condenser 12 is 5 ° C., and the operation in the evaporator 14 is performed. It carried out by setting the degree of superheating of the medium to 5 ° C., respectively. In addition, it was assumed that there was no pressure loss in equipment efficiency and piping and heat exchanger.

The refrigeration capacity Q and the coefficient of performance η can be obtained from the following equations (2) and (3) when the enthalpy h of each state (where the subscript h represents the state of the working medium).
Q = h _A -h _D (2)
η = Q / compression work = (h _A −h _D ) / (h _B −h _A ) (3)
The characteristic value of the thermodynamic property necessary for calculating the refrigeration cycle performance was calculated based on the generalized equation of state (Soave-Redrich-Kwong equation) based on the corresponding state principle and the thermodynamic relational equations. When characteristic values were not available, calculations were performed using an estimation method based on the group contribution method.

The coefficient of performance represents the refrigeration efficiency in the refrigeration cycle system 10, and the higher the coefficient of performance, the smaller the input (the amount of power required to operate the compressor) and the larger the output (refrigeration capacity). It represents what can be obtained.
On the other hand, the refrigeration capacity represents the ability to cool the load fluid, and the higher the refrigeration capacity, the more work can be done in the same system. In other words, the larger the refrigeration capacity, the more the target performance can be obtained with a small amount of working medium, and the system can be miniaturized.

[Evaluation of Global Warming Potential (GWP)]
The values of global warming potential of the working media used are also shown in Tables 5-7.
The global warming potential (100 years) of HFC-134a is 1430 according to the Intergovernmental Panel on Climate Change (IPCC) Fourth Assessment Report (2007), and the global warming potential of HFC-125 (100 The year is 3500. The global warming potential (100 years) of HFO-1123 is 0.3 as a value measured according to the IPCC Fourth Assessment Report. Moreover, GWP in a mixture is shown as a weighted average by a composition mass.

[Examples 18 to 52]
A ternary working medium prepared by mixing HFO-1123, HFC-134a, and HFC-125 so that the ratio when reaching the equilibrium state is as shown in Table 5 and Table 6 is shown in FIG. The refrigeration cycle performance (refrigeration capacity and coefficient of performance) was evaluated by applying to the cycle system 10.
The evaluation was performed by obtaining the relative performance (each working medium / R410A) of the refrigeration cycle performance (refrigeration capacity and coefficient of performance) of each working medium based on the refrigeration cycle performance when R410A was used as the working medium. The evaluation results are shown in Table 5 and Table 6.

As shown in Tables 5 and 6, a working medium in which HFC-134a was added to HFO-1123 was used so that the ratio of HFO-1123 in the gas phase formed in the system was 50% by mass or less. In Examples 18 to 26, the coefficient of performance was improved as compared with Example 52 using HFO-1123 alone as the working medium. In Examples 18 to 26, the refrigerating capacity was higher than that in Example 51 using HFC-134a alone as the working medium. In Examples 18 to 26, GWP is smaller than R404A (GWP: 3922) used for freezing and refrigeration.
In Examples 27 to 35 using a working medium in which HFC-125 was added to HFO-1123 so that the ratio of HFO-1123 in the gas phase formed in the system was 50% by mass or less, HFO was used as the working medium. Compared to Example 52 using -1123 alone, the coefficient of performance was the same and the refrigeration capacity decreased, but 0.77 or more was maintained. In addition, Examples 27 to 35 had a higher refrigeration capacity than Example 50 using HFC-125 alone as a working medium. In Examples 27 to 35, the GWP is smaller than that of R404A or the like used for freezing and refrigeration.
In addition, Examples 36 to 36 in which a working medium using HFC-134a and HFC-125 in combination with HFO-1123 so that the ratio of HFO-1123 in the gas phase formed in the system is 50% by mass or less are used. 47, the coefficient of performance was improved as compared with Example 52 where HFO-1123 alone was used as the working medium, and the sufficient refrigeration capacity was maintained, although the refrigeration capacity decreased. In Examples 36 to 47, the GWP is smaller than that of R404A or the like used for freezing and refrigeration.
In addition, the same tendency was observed in Examples 48 and 49 in which the proportion of HFO-1123 in the gas phase was more than 50% by mass, but the combustibility of these compositions was not sufficiently suppressed.

[Examples 53 to 93]
A four-component working medium prepared by mixing HFO-1123, HFC-125, HFO-1234yf, and HFC-134a in the proportions shown in Table 7 is applied to the refrigeration cycle system 10 of FIG. The refrigeration cycle performance (refrigeration capacity and coefficient of performance) was evaluated.
The evaluation was performed by obtaining the relative performance (each working medium / R410A) of the refrigeration cycle performance (refrigeration capacity and coefficient of performance) of each working medium based on the refrigeration cycle performance when R410A was used as the working medium. Table 7 shows the evaluation results.

As shown in Table 7, the ratio of HFO-1123 to 3% by mass to 35% by mass and the ratio of HFC-134a to the total amount of HFO-1123, HFC-134a, HFC-125, and HFO-1234yf is 10%. Examples 53 to 87 in which the ratio of HFC-125 is 4% by weight to 50% by weight and the ratio of HFO-1234yf is 5% by weight to 50% by weight are examples outside this range. It can be seen that the coefficient of performance and the refrigerating capacity are generally at a high level as compared to 88 to 93, and the GWP is suppressed to a lower level.

The heat cycle system of the present invention is useful in refrigerators, air conditioners, power generation systems (waste heat recovery power generation, etc.), latent heat transport devices (heat pipes, etc.) and the like.
It should be noted that the entire contents of the specification, claims, abstract and drawings of Japanese Patent Application No. 2014-044171 filed on March 6, 2014 are cited here as disclosure of the specification of the present invention. Incorporated.

DESCRIPTION OF SYMBOLS 10 Refrigeration cycle system 11 Compressor 12 Condenser 13 Expansion valve 14 Evaporator

Claims (13)

1. A working medium for heat cycle comprising trifluoroethylene and one or both of 1,1,1,2-tetrafluoroethane and pentafluoroethane,
   A working medium for heat cycle, wherein a ratio of trifluoroethylene to a total mass of the working medium is 42% by mass or less.
2. The working medium for heat cycle according to claim 1, wherein the ratio of the total amount of 1,1,1,2-tetrafluoroethane and pentafluoroethane to the total mass of the working medium is 58% by mass or more.
3. A working medium for thermal cycle comprising trifluoroethylene, 1,1,1,2-tetrafluoroethane, pentafluoroethane and 2,3,3,3-tetrafluoropropene,
   The ratio of the total amount of trifluoroethylene, 1,1,1,2-tetrafluoroethane, pentafluoroethane, and 2,3,3,3-tetrafluoropropene to the total mass of the working medium exceeds 90% by mass. 100% by mass or less,
   The ratio of trifluoroethylene to the total amount of trifluoroethylene, 1,1,1,2-tetrafluoroethane, pentafluoroethane and 2,3,3,3-tetrafluoropropene is 3% by mass or more and 35% by mass. Hereinafter, the proportion of 1,1,1,2-tetrafluoroethane is 10% by mass to 53% by mass, the proportion of pentafluoroethane is 4% by mass to 50% by mass, 2,3,3,3-tetrafluoro The working medium for heat cycle according to claim 1 or 2, wherein the proportion of propene is 5 mass% or more and 50 mass% or less.
4. The ratio of trifluoroethylene to the total amount of trifluoroethylene, 1,1,1,2-tetrafluoroethane, pentafluoroethane and 2,3,3,3-tetrafluoropropene is 6% by mass or more and 25% by mass. Hereinafter, the proportion of 1,1,1,2-tetrafluoroethane is 20% by mass to 35% by mass, the proportion of pentafluoroethane is 8% by mass to 30% by mass, 2,3,3,3-tetrafluoro The working medium for heat cycle according to claim 3, wherein the proportion of propene is 20 mass% or more and 50 mass% or less.
5. The thermal cycle working medium according to any one of claims 1 to 4, wherein the thermal cycle working medium has a global warming potential of 2000 or less.
6. A thermal cycle system using a working fluid for thermal cycle comprising trifluoroethylene and one or both of 1,1,1,2-tetrafluoroethane and pentafluoroethane,
   The thermal cycle system whose ratio of the trifluoroethylene in the gaseous phase formed in this thermal cycle system is 50 mass% or less.
7. The thermal cycle system according to claim 6, wherein a ratio of trifluoroethylene to a total mass of the working medium in the system is 42% by mass or less.
8. The thermal cycle system according to claim 6 or 7, wherein a ratio of a total amount of 1,1,1,2-tetrafluoroethane and pentafluoroethane to a total mass of the working medium in the system is 58% by mass or more. .
9. A thermal cycle system using a thermal cycle working medium comprising trifluoroethylene, 1,1,1,2-tetrafluoroethane, pentafluoroethane, and 2,3,3,3-tetrafluoropropene,
   The ratio of the total amount of trifluoroethylene, 1,1,1,2-tetrafluoroethane, pentafluoroethane, and 2,3,3,3-tetrafluoropropene to the total mass of the working medium exceeds 90% by mass. 100% by mass or less,
   The ratio of trifluoroethylene to the total amount of trifluoroethylene, 1,1,1,2-tetrafluoroethane, pentafluoroethane and 2,3,3,3-tetrafluoropropene is 3% by mass or more and 35% by mass. Hereinafter, the proportion of 1,1,1,2-tetrafluoroethane is 10% by mass to 53% by mass, the proportion of pentafluoroethane is 4% by mass to 50% by mass, 2,3,3,3-tetrafluoro The thermal cycle system according to any one of claims 6 to 8, wherein the proportion of propene is 5 mass% or more and 50 mass% or less.
10. The ratio of trifluoroethylene to the total amount of trifluoroethylene, 1,1,1,2-tetrafluoroethane, pentafluoroethane and 2,3,3,3-tetrafluoropropene is 6% by mass or more and 25% by mass. Hereinafter, the proportion of 1,1,1,2-tetrafluoroethane is 20% by mass to 35% by mass, the proportion of pentafluoroethane is 8% by mass to 30% by mass, 2,3,3,3-tetrafluoro The thermal cycle system according to claim 9, wherein the proportion of propene is 20% by mass or more and 50% by mass or less.
11. The thermal cycle system according to any one of claims 6 to 10, wherein a global warming potential of the working medium for thermal cycle is 2000 or less.
12. The thermal cycle system according to any one of claims 6 to 11, which is used for a refrigeration / refrigeration device, an air conditioning device, a power generation system, a heat transport device or a secondary cooler.
13. Room air conditioners, store packaged air conditioners, building packaged air conditioners, facility packaged air conditioners, gas engine heat pumps, train air conditioners, automotive air conditioners, built-in showcases, separate showcases, commercial refrigerators / refrigerators, ice machines The heat cycle system according to any one of claims 6 to 11, which is used in a vending machine.

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